Vat dyestuff and intermediated of the pyrene-quinone and perylenequinone series



Patented Feb. 19, 1935 i VAT DYEST'UFF \THE PYRENE-QUINONE AN D PERLENiE -"g l a 'QUIN ON E 1 SERIES Ralph N. Lulek and Melvin A. Perkins, Milwaukee, 1'

. .Wis., assignors to E. I. duPont de Nemours & Company, Wilmington, DeL, "a corporation oi;

Delaware No Drawing. Application April 10, 1933, i Serial No. 665,441 I M 20 Claims. (01. 260 -51).

This invention :relates to vat dyestuffs and intermediates therefor. i 1

It isan object of this invention to prepare novel compounds-of the pyrene-quinone and perylenequinone, series, some of which are usefulas;vat dyestufis,;'while the others may be used as intermediatesifor the manufacture ofotherorganic compounds. i I a. It is a further object of thisinvention to provide novel intermediates for the production. of the compounds aforementioned.

It is a further object of this invention to provide processes for the manufacture of said novel intermediates and for'conversion of the latter into compounds of the pyrene and perylene series.

Other and further important objects of this invention will appear as the description proceeds.

. The novel compounds" of thisinvention are derivable by ring closure from m-aroyl-anthracenes, and are characterized by possessing in their structure the configuration:

boxylic I acid chloride=23.4% Cl.)

and include intheirstructu're' either the pyrenequinone orthe perylene quinor'ie configuration; More particularly, the 1,4-diar0yl derivative leads to a compound of thepyrene-quinone structure; the 1,5-is0mer to a perylene-quinone; while the l,'10-derivativermay lead toeither a pyrene-quinone or a perylene-quinon'e', and most likely toa mixture of thetwo. a I

The ring closure, according to'our invention, may 'be efiected'by fusion: with ametal halide condensing agent" such as aluminum" chloride, preferably "in the presence of oxidizing agents. 'Most "of'ithe'. intermediates requisite for our process "are,'toithe bestof our knowledge, also novel compounds and form .an integral part of this; invention." --We' prepare these novel com pounds bystarting' with. the corresponding alpha anthracene-mono or di-carboxylic acid, converting the same into the corresponding monoor dicarbonyl-chloride, and then: reacting with an arcmatic hydrocarbon in the presence of a metallic halide condensing agent. In the case of the LIO-diarQyI-anthracene, the l-aroyl-anthracene is prepared'first as mentioned above, and then reacted with benzoylchloride in the presence of aluminum chloride.; I

Withoutlimiting ourjinvention to any particular procedure, the following examples are given to illustrate our specific mode of operation. Parts are by weight.

EXAMPLE 1 (c) Formation of acid chloride 15 parts of 1,4-anthracene-dicarboxylic acid,

obtained from the corresponding anthraquinoncdicarboxylic acidby, reduction with zinc and ammonia (Elbs. Journal fiir Praktische Chemie (2), 1. 30,.and 'Phillips, Journal of the-American ChemicalSociety, 46, 2533), are introducedinto 45 parts of waterfree benzolsat room temperature. 25 parts of phosphorus pentachloride are now added and the mixture is agitateduntil near- 1y, all in solution. Heat is then applied gently and the solution is heatedto reflux for about 15 minutes or until hydrochloric acid evolution I has ceased. The dark reddish solution is then allowed to cool-slowly, separating deep red crystals; flngitation is thenapplied and 'm parts of petroleum etherare added. The red crystals are filtered by suction, washedtwith petroleum ether parts) and dried. The yield is good and the deep red crystalline product analyzes-about 23% chlorine. (Theory for 1,4-anthracene-dicar- (b) Formation of ketorze 10 parts of the product of Step (a) are introduced into parts of water-free benzol, and 25 parts oi aluminum chloride are added in small portions at 20-25" C. over the course of one-half hour. The acid chloride goes rapidly into solution and the solution becomes dark. The solution is warmed to 50 C. over the course of one hour and maintained at 50-6'0 C- for three hours. At the end of this period, the mixture is allowed to cool and then poured onto ice (about 500 parts) to which hydrochloric acid (35 parts of sp. gr. 1.10 acid) has been added. The excess benzol is steamed oii, and the mass is allowed to cool. A brownish-yellow solid mass is obtained, which is ground up and agitated first;

with dilute hydrochloric acid, and then with dilute ammonia; and finally it is dried in the air. The product is most probably 1,4-dibenzoyl-anthracene. It is a light brownish-yellow solid giving an orange coloration in sulfuric acid, and being very soluble in the common organic solvents.

(c) Ring closure 10 parts of the diketone obtained in Step (b) are stirred into 100 parts of molten anhydrous sodium-aluminum chloride at C., and the melt is maintained at this temperature with stirring and introductionof a slow stream of oxygen for a period of 24 hours. The melt is then hydrolyzed by pouring onto ice, containing hydrochloric acid, and the mass heated, filtered, and the brown residue washed free of acid. -The product forms a brown powder which is not soluble in alkaline hydrosulfite solution. Itis most probably a pyrene-quinone derivative of the formula:

EXAMPLE 2 (a) Formation of acid chloride The reaction is allowed to proceed Without external application of heat for one hour, after which heat is applied gently. The solid gradually goes into solution. Heating is continued until the solution. has refluxed for about one-half hour or until hydrochloric acid evolution ceases.

Upon cooling, greenish-yellow crystals appear! The mass'is diluted with an equal volume of petroleum ether, filtered, and the 1,5-anthracenedicarboxylic acid chloride washed with petroleum ether and dried. It forms a dull green-yellow powder and contains a quantity of chlorine corresponding to two atoms.

(b) Formation of ketone The diketone thus obtained tense grass-green coloration in sulfuric acid. A similar product is obtained by using toluol in place of benzol in-this example.

(0) Ring closure An intimate mixture, made by grinding together 10 parts of the product of Step (b), 10

parts of manganese dioxide and 100 parts of anhydrous aluminum chloride, is fused and heated at 160-170" C. for about three hours.

Copious evolution of hydrochloric acid takes place. The

melt is then hydrolyzed as usual for this type of reaction (see Example 1 .(c) ),excess' manganese dioxide is destroyed by treatment with sulfur dioxide, and the violet solid remaining is filtered off, washed and dried. It forms "a dense copperyblue solid which. dissolves inconcentrated 'Sulr furic acid'with-a grass green color and in'alk aline hydrosulfite with a. bluish-green color. 3 Cute ton is dyed in reddish-violet shades of good Inst mess. The dyestuff is probably a dibenz-perylenequinone of .the formula: l.

The same product is obtained by using other I oxidizing agents, such as air,'or oxygen, in place of manganese dioxide, or again in the absence of. any added oxidizing agent whatever.

EXAM1I.-E 3 I (a) Formation of acid chloride. and monoketone 10 parts of alpha anthracene-carboxylic acid are suspended in 100 parts of bench and 9 of phosphorus 'pen'ta-chloride are added. The

mass is warmed gradually,-boiled-for one-half hour, cooled to 15 C., an'd 15 parts of anhydrous aluminum chloride are added in small portions. After one-half hour at 1520 C. the temperature is gradually raised to 50C. and maintained I at that value for one hour. The mass is then cooled, drowned in dilute hydrochloric acid, steam distilled and worked up asin Example 1. It constitutes most probably 1-benzoyl-anthracene.

(b) Formatiortofdiketone 1 part of this compound is next suspended in 10 parts of nitrobenzol. To this suspension,

part of benzoyl chloride and 1% parts of alumi- 1 num chloride are added at room temperature; After one-half hour,the'ftemperature is gradual ly raised to 60 C. and maintained at this value for two hours. After drowning in dilute hydrochloric acid, the nitrobenzoyl is steamed or: and,

the residue is extracted with alcohol. It consists, most probably, of 1,10-dibenzoyl-anthracene.

The same compound may also be obtained by benzoylating alphaanthracene-carboxylic acid in nitrobenzene and converting the benzoyl-anthracene-carboxylicacid thus obtained to the dibenzoyl-anthracene through the acid chloride and condensation of the latter'with benzol in accordance with procedures already described.

(c) 'Ri1ig closure 7 r r v 1 part of the product of Step (b) (either method) is intimately mixed with 5 to 7 parts of sodium aluminum chloride, and the mixture is fused at -180" C. for about 10 hours.- Oxidizing agents may be added if desired. After- 10 hours, the melt is drowned and worked up in the usual manner. Thenew ketonic hydrocarbon is not soluble'in alkalinehydrosulfite solu tion but is different fromthe starting material. It is most probably a mixture of two compounds represented by the following formulast It will be understood that many variations and modifications are possible in the specific procedures above set forth without departing from the spirit of this invention.

For instance, the formation of the anthracene acid chlorides may be modifiedaccording to any well known procedure for preparing acid chlorides from the corresponding carboxylic acids. Thus, instead of benzol, phosphorus oXy-chloride may be used as solvent. Or the solvent may be omitted altogether, the reactants being merely fused together. Instead of phosphorus pentachloride, thionyl chloride may be used as chlorinating agent.

Again, after formation of the anthracene acid chlorides, the latter may be isolated as described and further treated with benzol and aluminum chloride to form the corresponding anthracenephenyl-ketone, or aluminum chloride may be added directly to the mass in which the acid chloride was formed, causing the latter to react with the benzol which had been employed heretofore as solvent.

Instead of benzol, toluol, naphthalene or other cyclic aryl compounds may be used to form the corresponding anthracene aryl-mono-ketone or di-ketone.

In the aluminum chloride fusion the time and temperature may be varied within wide limits, as will be understood from analogous fusions known in the art. Sodium chloride may be added to reduce the fusion point of the mass. Oxidizing agents such as manganese dioxide or potassium chlorate may be added to facilitate ring closure, or a stream of oxygen or air may be conductedthrough lthe' molten mass; Or again; the" oxidizing "agent maybe omitted altogether; the contact of the fused mass' with the atmosphere being sufiicient to effect the requisite degree of oxidation. 1

We claim:

1-. A compound of the general formula:

said compound being substantially identical with the compound obtainable by ring closing by the aid of aluminum chloride in the presence of an oxidizing agent an a: 1 diaroyl anthracene where x designates the 4, 5 or 10 position.

2. A perylene-quinone derivative of the generalformula: l

said derivative being substantially identical with the compound obtainable by ring closing a 1,5- diaroyl-anthracene.

3. 'Dibenz-perylene-quinone, being substantially identical with the compound obtainable by ring closing 1,B-dibenzoyl-anthracene.

4. The process of producing a ketonic compound of the anthracene series; which comprises fusing with aluminum chloride an alpha-aroylanthracene selected from the group consisting of alpha-mono-aroyl-anthracene and x, l-diaroyl-anthracene, wherein m designates the 4, 5 or 10 position in the anthracene molecule.

5. A process as in claim 4, the'fusion being carried out in thepresence of an oxidizing agent.

6. The process of producing a ketonic compound of the anthracene series, whichcomprises fusing with aluminum chloride m, 1-diaroyl-an-. thracene, wherein a: designates the 4, 5 or 10 position in the anthracene molecule.

'7. A process as in claim 6, the fusion being carried out in the presence of an oxidizing agent.

8. The process of producing a ketonic compound of the anthracene series, which comprises fusing with aluminum chloride a 1,5-diaroylanthracene.

carried out in the presence of an oxidizing agent selected from the group comprising manganese dioxide, oxygen and air. .10. A process as. in claim 8, thefusion bein carried out in the presence of manganese dioxide.

11. The process of producing a ketonic compound of the anthracene series, which comprises fusing with aluminum chloride 1,5-dibenzoylanthracene.

12. The process of producing a ketonic compound of the anthracene series, which comprises fusing with aluminum chloride, in the presence of manganese dioxide, 1 ,5-dibenzoyl-anthracene, hydrolyzing the intermediate organic aluminum chloride complex thus formed by the aid of dilute aqueous hydrochloric acid, destroying the excess of manganese dioxide, and recovering the precipitated organic compound.

13. An intermediatefor dyestuffs having the general formula:

anthracene-carbonyl-halide with. an aromatic hydrocarbon in the presence of a metal halide condensing agent. r

18. The, process .of producing a diaroyl-anthracene compound which comprises. reacting an anthracene-dicarbonylchloride with anexcess of, aromatic hydrocarbon in the presence 0! a metallic chloride condensing agent.

I 19. The process of producing a 1,5-diaroyl-an-I thracene, which comprises reacting 1,5-anthracene-dicarbonyl-chloride with: an excess of an.

aromatic hydrocarbon in the presenceof alu-i minum chloride. ,1 I

20. The process ofv producing 1,5-dibenzoyle anthracene, which comprises reacting 1,5-anthracene-dicarbonyl-chloride with" an excess of V c 25' benzene in the presence of aluminum chloride.

RALPHN. LULEK. MELVIN; A. PERKINS. 

